DESCRIPTION
Title of Invention
REGENERATED HYDROTREATMENT CATALYST
Technical Field
5 [0001] The present invention relates to a regenerated hydrotreatment
catalyst having superior catalyst performance for treating a petroleum
fraction.
Background Art
[0002] Sulfur-containing compounds, nitrogen-containing compounds,
10 oxygen-containing compounds, and the like are contained in crude
`petroleum as impurities, and as to petroleum fractions obtained through
a step such as distillation from the crude oil, the contents of these
impurities are reduced by a step of bringing the fractions into contact
with a catalyst having hydrogenation activity in the presence of
15 hydrogen, the step being referred to as hydrotreatment. Desulfurization,
for reducing the contents of the sulfur-containing compounds, is
especially well known. Recently, in terms of reducing environmental
load, there have been stricter demands for controlling or reducing the
contents of impurities including sulfur-containing compounds in
20 petroleum products, and a large number of so-called "sulfur-free"
petroleum products are being manufactured.
[0003] After a hydrotreatment catalyst used for hydrotreatment of a
petroleum fraction is used for a certain period of time, its activity is
lowered due to the deposition of coke or sulfur components and the like,
25 and replacement is therefore carried out. Especially due to the increase
in demand for "sulfur-free" petroleum products, a greater hydrotreating
FP10.0588-00
capability is required in hydrotreating facilities for petroleum fractions
such as kerosene, gas oil and vacuum gas oil, which increases the
frequency of catalyst replacement , resulting in increased catalyst costs
and a greater amount of waste catalyst.
5 [0004] As a countermeasure, a regenerated catalyst regenerated from a
spent hydrotreatment catalyst is partially used in these facilities (For
example, see Patent Literatures 1 and 2).
Citation List
Patent Literature
10 [0005] [Patent Literature 1] Japanese Patent Application Laid-open No.
S52-68890
[Patent Literature 2] Japanese Patent Application Laid-open No.
H5-123586
Summary of Invention
15 Technical Problem
[0006] In the use of a regenerated catalyst, if the activity of a
hydrotreatment catalyst could be maintained even when hydrotreatment
and regeneration are performed several times, the merit in using a
regenerated catalyst for hydrotreatment (hereinafter, referred to as
20 "regenerated hydrotreatment catalyst" or simply "regenerated catalyst")
is further increased . However, in the regeneration of a spent catalyst for
hydrotreatment (hereinafter, referred to as "spent hydrotreatment
catalyst" or simply "spent catalyst"), the regeneration can recover the
catalytic activity in terms of coke deposition which is one of the causes
25 for lowering the activity of the hydrotreatment catalyst, but the
regeneration itself may cause the catalytic activity to be lowered.
2
FP10-0588-00
Furthermore, the activity after regeneration may depend on the history
of use before regeneration, regeneration methods, and the like, and
therefore, a regenerated catalyst, especially a regenerated catalyst which
has been regenerated multiple times, does not always exhibit stably
5 sufficient activity. Also, there may be cases where it is necessary to
select regeneration conditions according to the history of the spent
catalyst. In the case where a regenerated catalyst is proven to have low
activity after a hydrotreatment operation is initiated by packing a
hydrotreatment facility with the regenerated catalyst, it is very
10 problematic because the reduction of the treatment speed of an oil feed
stock, and so on are necessary.
[0007] The present invention has been made to solve the
above-described problem, and an object of the present invention is thus
to provide a regenerated catalyst having excellent desulfurization
15 activity and a method of manufacturing petroleum products using the
same.
Solution to Problem
[0008] To solve the problems above, the present invention peovides a
regenerated hydrotreatment catalyst regenerated from a hydrotreatment
20 catalyst for treating a petroleum fraction , the hydrotreatment catalyst
being prepared by supporting molybdenum and at least one species
selected from metals of Groups 8 to 10 of the Periodic Table on an
inorganic carrier containing an aluminum oxide, wherein a residual
carbon content is in the range of 0.15 mass% to 3.0 mass %, a peak
25 intensity of a molybdenum composite metal oxide with respect to an
intensity of a base peak is in the range of 0.60 to 1.10 in an X-Ray
3
FP1O-0588-00
diffraction spectrum, and a peak intensity of a Mo-S bond derived from
a residual sulfur peak with respect to an intensity of a base peak is in the
range of 0.10 to 0.60 in a radial distribution curve obtained from an
Extended X-ray Absorption Fine Structure (EXAFS) spectrum of an
5 X-ray Absorption Fine Structure (XAFS) analysis, and the present
invention also provides a regenerated hydrotreatment catalyst
regenerated from a hydrotreatment catalyst for treating a petroleum
fraction, the hydrotreatment catalyst being prepared by supporting
molybdenum and at least one species selected from metals of Groups 8
10 to 10 of the Periodic Table on an inorganic carrier containing an
aluminum oxide, wherein a residual carbon content is in the range of
0.15 mass% to 3.0 mass%, a peak intensity of a molybdenum composite
metal oxide with respect to an intensity of a base peak is in the range of
0.60 to 1.10 in an X-Ray diffraction spectrum, and a ratio of M003 is in
15 the range of 77% to 99% in an X-ray Absorption Near-Edge Structure
(XANES) spectrum of an X-ray absorption fine structure analysis.
[0009] The present invention also provides a method of manufacturing
petroleum products, wherein hydrotreatment of a petroleum fraction is
performed using the regenerated hydrotreatment catalyst of the present
20 invention.
[0010] In the method of manufacturing petroleum products, conditions
of the hydrotreatment of the petroleum fraction should preferably be a
hydrogen partial pressure in the range of 3 to 13 MPa, LHSV in the
range of 0.05 to 5 h", a reaction temperature in the range of 200°C to
25 410°C, a hydrogen/oil ratio in the range of 100 to 8,000 SCF/BBL, and
a boiling point in the range of 130°C to 700°C of the petroleum fraction
4
FP10®0588-00
used as an oil feed stock.
Advantageous Effects of Invention
[0011] The present invention provides the effect in which a highly
practical manufacturing process can be realized using a regenerated
5 catalyst which has sufficient activity and is low-priced for the
manufacture of petroleum products , and is very useful for cost
reduction, reducing the amount of discharged waste , making
hydrotreatment of petroleum fractions efficient, and so on.
Brief Description of Drawings
10 [0012] Fig. 1 is a drawing for explaining how to determine the presence
or absence of a composite oxide.
Fig. 2 is a drawing for explaining an XAFS analysis method.
Fig. 3 is a drawing for explaining how to determine a Mo-S bond
strength.
15 Fig. 4 is a drawing for explaining how to determine a ratio of Mo®3.
Description of Embodiments
[0013] Hereinafter, preferred embodiments of the present invention will
be described below in detail.
[0014] (Hydrotreatment catalyst)
20 An-unused hydrotreatment catalyst (hereinafter, referred to as "unused
catalyst") corresponding to a regenerated hydrotreatment catalyst of the
present invention includes at least one species selected from metals of
Groups 8 to 10 of the Periodic Table , and molybdenum (hereinafter,
these are collectively referred to as "active metal" ). Iron, cobalt or
25 nickel is preferable as the metal of Groups 8 to 10 of the Periodic Table;
cobalt or nickel is more preferable ; and cobalt is especially preferable.
5
FP 10®058800
The metal of Groups 8 to 10 of the Periodic Table and molybdenum
may be respectively used alone, or used in combination of at least two
species thereof. Specifically, molybdenum-cobalt, molybdenum-nickel,
molybdenum-cobalt-nickel, and the like may be preferably used as the
5 combination of the metals. The Periodic Table described herein is the
long-form periodic table defined by the IUPAC (International Union of
Pure and Applied Chemistry).
[0015] The unused catalyst is a catalyst in which the active metal is
supported on an inorganic carrier containing aluminum oxide. Preferred
10 examples of the inorganic carrier containing aluminum oxide may
include alumina, alumina-silica, alumina-boria, alumina-titania,
alumina-zirconia, alumina-magnesia, alumina-silica-zirconia,
alumina-silica-titania, and a carrier obtained by adding, into alumina, a
porous inorganic compound of various types of clay minerals such as
15 zeolite, sepiolite and montmorillonite. Among these examples, alumina
is particularly preferable.
[0016] The unused catalyst is preferably obtained by supporting 10 to
30 mass% of molybdenum as an oxide and 1 to 7 mass% of at least one
species (for example, cobalt and/or nickel) selected from the metals of
20 Groups 8 to 10 of the Periodic Table as an oxide, on an inorganic carrier,
based on a total mass of the catalyst.
[0017] Although a precursor of active metal species used in supporting
the active metal on the inorganic carrier is not specifically limited, an
inorganic salt, an organic metal compound, or the like of the metal is
25 used as the precursor, and a water-soluble inorganic salt is preferably
used as the precursor. A supporting process is preferably performed
6
FP10-0588-00
using a solution, preferably aqueous solution, of the active metal
precursor. Preferably, the supporting process adopts publicly-known
methods such as dipping, impregnation, and co-precipitation.
[0018] The carrier on which the active metal precursor is supported is
5 calcined preferably in the presence of oxygen after being dried, and it is
preferable that the active metal species is first made into an oxide.
Furthermore, before petroleum fractions are hydrotreated, a process of
making the active metal into a sulfide through a sulfiding treatment
called presulfiding is preferably performed.
10 [0019] (Hydrotreatment process)
In a hydrotreatment process of petroleum fractions, a catalyst filled into
a facility is preferably subjected to a presulfiding treatment prior to a
hydrotreatment reaction using a sulfur compound to thereby make an
active metal species into a metal sulfide.
15 [0020] Although the presulfiding conditions are not specifically limited,
the presulfiding treatment is preferably performed in such a manner that
a sulfur compound is added to an oil feed stock used for hydrotreatment
of petroleum fractions, and the resultant mixture is continuously brought
into contact with the regenerated catalyst under conditions in which the
20 temperature is in the range of 200 to 380°C, LHSV is 1 to 2 If', the
pressure is set equal to that of hydrotreatment, and the treatment times is
48 hours or more. The sulfur compound added to the oil feed stock is
not specifically limited, but preferably includes dimethyl disulfide
(DMDS), hydrogen sulfide and the like, and is preferably added in an
25 amount of 1 mass% based on the mass of the oil feed stock.
[0021 ] The operating conditions for hydrotreatment of petroleum
7
FP10-0588 00
fractions are not specifically limited. Thus, a small quantity of the sulfur
compound such as MMS may be added to the oil feed stock for the
purpose of allowing the active metal species of the catalyst to keep its
sulfide state; however, it is desirable that the sulfur compound is not
5 added particularly because the sulfur compound which has already been
contained in the oil feed stock typically makes it possible to keep the
sulfide state.
[0022] The hydrogen partial pressure at an inlet of a reactor in the
hydrotreatment process is preferably 3 to 13 MPa, more preferably 3.5
10 to 12.MPa, and particularly preferably 4 to 11 MPa. If the hydrogen
partial pressure is less than 3 MPa, coke is more actively produced on
the catalyst, and the life of the catalyst tends to be shortened. On the
contrary, if the hydrogen partial pressure exceeds 13 MPa, the
construction cost for a reactor or peripheral facilities may be increased
15 and is thus economically infeasible.
[0023] The hydrotreatment process may be performed under the
conditions in which LHSV is in the range of preferably 0.05 to 5 h-1,
more preferably 0.1 to 4.5 h"1, and particularly preferably 0.2 to 4 h"1. If
LHSV is less than 0.05 h"1, the construction cost for a reactor becomes
20 too high and is therefore economically infeasible. On the contrary, if
LHSV is greater than 5 h-1, an oil feed stock may not be sufficiently
hydrotreated.
[0024] The hydrogenation reaction temperature in the hydrotreatment
process is preferably 200°C to 410°C, more preferably 220°C to 400°C,
25 and particularly preferably 250°C to 395°C. If the reaction temperature
is less than 200°C, an oil feed stock tends to be insufficiently
8
FP10-0555-00
hydrotreated. If the reaction temperature is higher than 410°C, it is
undesirable because the yield of a target refined oil is decreased due to
an increase in the amount of by-produced gas.
[0025] The hydrotreatment process may be performed under the
5 conditions in which a hydrogen/oil ratio is in the range of 100 to 8,000
SCF/BBL, more preferably 120 to 7,000 SCF/BBL, and particularly
preferably 150 to 6,000 SCF/BBL. If the hydrogen/oil ratio is less than
100 SCF/BBL, coke is produced on the catalyst at an outlet of the
reactor, thus shortening catalyst life. In contrast, if the hydrogen/oil ratio
10 exceeds 8,000 SCF/BBL, the construction cost for a recycle compressor
'becomes too high, and is thus economically infeasible.
[0026] Although the reaction type in the hydrotreatment process is not
specifically limited, it may be typically selected from various types of
processes such as a fixed bed and a moving bed process, and
15 particularly, the fixed bed process is preferable. Also, the reactor
preferably has the shape of a tower.
[0027] The oil feed stock used for hydrotreatment of petroleum
fractions may have a distillation temperature (boiling point) measured
by a distillation test being in the range of preferably 130 to 700°C, more
20 preferably 140 to 650°C, and particularly preferably 150 to 660°C. If
the oil feed stock having the distillation temperature lower than 130°C
is used, the hydrotreatment reaction is carried out in a gaseous phase,
and the catalyst tends to not exhibit its performance sufficiently. On the
contrary, if the oil feed stock having the distillation temperature higher
25 than 700°C is used, the content of toxic substances such as heavy metals
contained in the oil feed stock with respect to the catalyst becomes
9
FPI0-0555-00
great, reducing the life of the catalyst significantly. Although other
properties of petroleum fractions used as the oil feed stock are not
specifically limited, representative properties are as follows: density at
15°C is in the range of 0.5200 to 0.9700 g/cm3; and sulfur content is in
5 the range of 1.0 to 4.0 mass%.
[0028] Sulfur content means a content of sulfur which is measured
according to "6. Energy-dispersive X-ray fluorescence Metod" of
"Crude Oil and Petroleum Products- Determination of Sulfur Content"
defined in JIS K 2541-1992. Distillation test means a test carried out
10 according to "6. Determination of Distillation Characteristics at
Reduced Pressure" of "Petroleum Products-Determination of
Distillation Characteristics" defined in JIS IC 2254. Density at 15°C
means a density measured according to "5. Oscillating Type Density
Test Method" of "Crude Petroleum and Petroleum Products -
15 Determination of Density and Petroleum Measurement Tables based on
a reference temperature (15°C)" defined in JIS K 2249.
[0029] (Regeneration process)
The facility for performing regeneration to produce a regenerated
catalyst is not specifically limited, but the regeneration is preferably
20 performed in another facility differing from the hydrotreatment facility
for petroleum fractions. That is, the regeneration is not performed in a
state in which the catalyst is still packed inside a reactor of the
hydrotreatment facility for petroleum fractions, but the regeneration is
preferably performed in such a manner that the catalyst is removed from
25 the reactor, the removed catalyst is then transferred to a regeneration
facility, and the regeneration is then carried out in the regeneration
10
FP10-0588-00
facility.
[0030] The method of regenerating the spent catalyst is not specifically
limited, but preferably includes processes in the order of a process of
removing pulverized catalyst from the spent catalyst or fillers other than
5 the catalyst if necessary by using a sieve, a process (deoiling process) of
removing oil adhered to the spent catalyst, and a process (regeneration
process) of removing coke, sulfur components, and the like which are
deposited on the spent catalyst.
[0031] Among these processes, the deoiling process preferably adopts a
10 method of volatilizing oil components by heating the spent catalyst at a
temperature of 200 to 400°C in a substantially oxygen-free atmosphere -
for example, a nitrogen atmosphere. Also, the deoiling process may be
performed using a method of cleaning oil components in light
hydrocarbons or a method of removing oil components by steaming.
15 [0032] The regeneration process preferably adopts a method of
oxidizing and removing deposited coke, sulfur components, and the
like, by heating the spent catalyst at a temperature of 250 to 700°C,
preferably 320 to 550°C, more preferably 330 to 450°C, and particularly
preferably 340 to 400°C in an atmosphere in which molecular oxygen is
20 present - for example, in the air, and especially in the flow of air. When
the heating temperature is lower than the lower limit temperature, the
removal of substances, such as coke and sulfur components which
deteriorated the catalytic activity, tend not to be effectively performed, a
decrease in a peak intensity of Mo-S bond of molybdenum sulfide
25 tend to be small, and a ratio of molybdenum oxide tend to be small. On
the contrary, when the heating temperature is higher than the upper limit
11
FP 10-0588-.00
temperature, the activity of a regenerated catalyst obtained tends to be
lowered because an active metal in the catalyst forms a composite metal
oxide and causes agglomeration.
[0033] Furthermore, the temperature of the regeneration process
5 preferably falls within a predetermined temperature range as calculated
below in addition to the above-described temperature range.
That is, the predetermined temperature is preferably with the range of
T1-30°C to T2+30°C, wherein Ti and T2 are determined by subjecting
the spent hydrotreatment catalyst to differential thermal analysis,
10 converting differential calories observed in a measuring temperature
range of 100°C to 600°C into differences in electromotive force, then
differentiating the differences in electromotive force twice by
temperature to obtain the smallest extreme value and the second
smallest extreme value, and taking the temperature corresponding to the
15 extreme value located in the lower-temperature range as Ti and the
temperature corresponding to the extreme value located in the
higher-temperature range as T2. By setting the regeneration temperature
to the predetermined temperature range above, it is easy to convert the
active metal in a sulfide state into an oxide state by use of the spent
20 catalyst, and it is also possible to prevent the decrease in activity of the
regenerated catalyst to a high degree, which may be caused by the
complete removal of coke deposited on the catalyst through combustion.
[0034] Furthermore, the lower limit of the temperature range is
preferably T1-20°C or higher, and particularly preferably T1-10°C or
25 higher, and the upper limit of the temperature range is preferably
T2+20°C or lower, and particularly preferably T2+10°C or lower.
12
FPIO-0588-00
[0035] The regeneration time is preferably 0.5 hours or longer, more
preferably 2 hours or longer, further more preferably 2.5 hours or
longer, and particularly preferably 3 hours or longer. If the regeneration
time is less than 0.5 hours, substances which deteriorated the catalyst
5 activity, e.g., coke, sulfur substances, and the like tend not to be
effectively removed.
[0036] (Regenerated catalyst)
Based on the mass of the regenerated catalyst, the lower limit of a
residual carbon content in the regenerated catalyst obtained through the
10 regeneration process is preferably 0.15 mass% or higher, more
preferably 0.4 mass% or higher, and particularly preferably 0.5 mass%
or higher; and the upper limit of the residual carbon content is
preferably 3.0 mass% or less, more preferably 2.5 mass% or less, and
particularly preferably 2.0 mass% or less. If the residual carbon content
15 is less than 0.15 mass%, the catalyst undergoes a thermal history during
the regeneration process to cause active metals to be agglomerated, and
thus, the activity of the regenerated catalyst tends to be lowered. In
contrast, if the residual carbon content is greater than 3.0 mass%, the
carbon blocks active sites of the catalyst and therefore the activity of the
20 regenerated catalyst tends to be lowered. "Residual carbon" described
herein is carbon (coke) remaining in the regenerated catalyst after
regenerating the spent hydrotreatment catalyst, and the residual carbon
content in the regenerated hydrotreatment catalyst was measured
according to "Coal and Coke-Mechanical Methods for Ultimate
25 Analysis" defined in JIS M 8819.
[0037] In a spectrum obtained by subjecting the regenerated catalyst to
13
FP10-0588-00
an X-ray diffraction analysis, a peak intensity derived from a
molybdenum composite metal oxide, which includes molybdenum and
at least one species selected from metals of Group 8 to 10 of the
Periodic Table, has a lower limit of preferably 0.60 or higher, more
5 preferably 0.70 or higher, and particularly preferably 0.75 or higher, and
has an upper limit of preferably 1.10 or lower, more preferably 0.90 or
lower, and particularly preferably 0.55 or lower, with respect to the
intensity of a base peak. If the peak intensity is less than 0.60, it is
undesirable because the oxidation of the regenerated catalyst is
10 insufficient to reduce the activity of the regenerated catalyst; and, if the
peak intensity is greater than 1.10, it is also undesirable because
molybdenum composite oxides agglomerate to reduce the activity of the
regenerated catalyst.
[0038] Furthermore, in a radial distribution curve obtained from an
15 EXAFS (Extended X-ray Absorption Fine Structure) spectrum obtained
by subjecting the regenerated catalyst to an XAFS analysis, the peak
intensity of Mo-S bond derived from residual sulfur has a lower limit of
0.10 or higher, preferably 0.12 or higher, and more preferably 0.15 or
higher, and has an upper limit of 0.60 or lower, and preferably 0.50 or
20 lower with respect to the intensity of the base peak. If the bond strength
is less than 0.10, it is undesirable because the structure of the
molybdenum oxide is changed to reduce the activity of the regenerated
catalyst; and if the bond strength is greater than 0.60, it is also
undesirable because sulfide compounds of molybdenum agglomerate to
25 reduce the activity of the regenerated catalyst.
[0039] A ratio of M003 which is obtained by analyzing the spectrum of
14
FP10=0588-00
an X-ray absorption near-edge structure region obtained by subjecting
the regenerated catalyst to the XAFS analysis has a lower limit of 77%
or higher, preferably 80% or higher, and more preferably 85% or higher,
and has an upper limit of 99% or lower, and preferably 95% or lower. If
5 the ratio of M003 is less than 77%, it is undesirable because sulfide
compounds of molybdenum agglomerate to reduce the activity of the
regenerated catalyst; and if the ratio exceeds 99%, it is also undesirable
because the structure of the molybdenum oxide is changed to reduce the
activity of the regenerated catalyst.
10 [0040] (Method for assessing regenerated catalyst)
'Hereinafter, a method for assessing a regenerated catalyst will be
described with reference to Figs. 1 to 4.
Fig. 1 is a result obtained by subjecting a sample to X-Ray Diffraction
(XRD) analysis.
15 In the X-ray diffraction patterns, by focusing on an XRD peak of
20=26.5±2° attributed to a molybdenum composite metal oxide which is
assumed from the active metal species contained in the catalyst obtained
through the regeneration process, the presence or absence of the
composite metal oxides is determined from a ratio of the peak intensity
20 (CPS: Counts Per Secound) to the intensity of a base peak of
20=66.8±2°.
The determination of the presence or absence of the peaks is preferably
performed according to the following criteria . That is, from the XRD
patterns of the regenerated catalyst, when a maximum intensity point of
25 A1203 of 20=66.812° as a base peak is denoted as Ha and a maximum
intensity point of 20=26.5±2° as a peak derived from the composite
15
FP10-0588-00
metal oxide is denoted as Ism, a peak intensity of the molybdenum
composite metal oxide with respect to the intensity of the base peak is a
value of Hni/Ha, wherein a baseline is taken as a straight line obtained
by connecting two points of a minimum intensity point I in the range of
5 20=13 to 16°, and a minimum intensity point II in the range of 20=69 to
73 °.
[0041] Typical conditions of XRD analysis are as follows.
X-ray source: CuKa
Divergence slit: 1/2°
10 Receiving slit: 0.15 mm
Scattering slit: 1/2°
20: 10 to 90°
Step width: 0.02°
Tube voltage: 50 kV
15 Tube current: 200 mA
Use of monochromator
Scanning mode: Continuous scanning
Scanning speed: 1 °/min
[0042] Fig. 2 is a result obtained by subjecting a sample to X-ray
20 Absorption Fine Structure (XAFS) analysis.
In this XAFS spectrum, an Extended X-ray Absorption Fine Structure
(E S) region of the catalyst obtained through the regeneration
process is a region having a higher energy level than a region
(absorption edge) where an X-ray absorption rate is dramatically
25 changed against the energy of irradiated X-rays, and the region is
Fourier transformed to obtain an EXAFS radial distribution curve
16
FF10-0588-00
shown in Fig. 3. From the EXAFS radial distribution curve, information
regarding a peripheral structure of an atom to be measured can be
obtained.
The XAFS analysis is a method of analyzing a structure of an analyte by
5 means of an absorption spectrum in which an X-ray absorption
coefficient of the analyte is plotted against X-ray energy, wherein the
analyte is irradiated with X-rays included in synchrotron radiation
generated from an electron accelerator or X-rays corresponding thereto
after changing the energy of the X-rays.
10 [0043] In the EXAFS radial distribution curve shown in Fig. 3, XAFS
measurement is carried out by focusing on molybdenum (Mo K
absorption edge) of active metals included in the regenerated catalyst. In
the radial distribution curve obtained through Fourier transformation of
the EXAFS region of the obtained spectrum, by focusing on a peal-,
15 intensity of Mo-S bond of an interatomic distance of 0.20 nm±0.01
which is attributed to a bond of a molybdenum atom-sulfur atom
derived from residual sulfur, the peak intensity of Mo-S bond is
determined from a ratio of the peak intensity to the intensity of'the base
peak of an interatomic distance of 0.13 nm±0.01. The determination of
20 the-peals intensity is performed preferably according to the following
criteria. That is, the EXAFS radial distribution curve is obtained by
extracting an EXAFS region using an XAFS analysis software, e.g.,
REX2000 (made by Rigaku), from the spectrum of the regenerated
hydrotreatment catalyst obtained through XAFS measurement, and then
25 performing Fourier transformation.
In this EXAFS radial distribution curve, when the peak derived from an
17
FP10-0588-00
Mo-S bond which is attributed to residual sulfur components is denoted
as a maximum intensity point Hs of the interatomic distance of 0.20
nm±0.01, and the base peak is denoted as a maximum intensity point Ho
of the interatomic distance of 0.13 nmf0.01 derived from an Mo-O
5 bond, a value of Hs/Ho is the peak intensity of the Mo-S bond to the
intensity of the base peak.
[0044] Also, the intensity of a peak in the radial distribution curve
obtained from the Extended X-ray Absorption Fine Structure region of
the spectrum acquired by performing the XAFS analysis is set as the
10 height of the peak. Also, details of data analysis such as a method of
taking a baseline for calculating the height of the peak were performed
using an integrated XAFS analysis software, X2000 (made by
Rigaku), according to methods disclosed in "57-61 pp., X-ray
absorption spectroscopy-XAFS and its applications-edited by Toshiaki
15 OTA and published by IPC (2002)".
[0045] The XAFS analysis of the regenerated catalyst of the present
invention is carried out by the method below.
X-ray source: Continuous X-ray
Spectral crystal: Si(3 11)
20 Beam size: l mm X 2 mm
Detector: Ionization chamber
Measurement atmosphere: air
Dwell time: 1 see
Measurement range: Mo K absorption edge (19974.0 to 20074.0 eV)
25 Data analysis (Fourier transformation) program: REX2000 (made by
Rigaku)
18
FP10-0588-00
[0046] In the XAFS spectrum of Fig. 2, an X-ray Absorption Near-Edge
Structure (XANES) region of the regenerated catalyst obtained through
the regeneration process is a region (absorption edge) where an X-ray
absorption coefficient is dramatically changed against the irradiated
5 X-ray energy, and an XANES spectrum shown in Fig. 4 is obtained by
analyzing the spectrum of this region. From the XANES spectrum,
information regarding the chemical status of an atom to be measured
can be obtained.
[0047] In the XANES spectrum shown in Fig. 4, XAFS measurement is
10 carried out by focusing on molybdenum (Mo K absorption edge) of
active metals included in the regenerated catalyst. In the XANES region
spectrum obtained, a ratio of MoO3 is determined by pattern fitting
using reference samples of MoO3 and MoSZ measured under the same
conditions. The determination of the spectrum is performed preferably
15 according to the following criteria. That is, a ratio of MoO3 is a ratio of
MoO3 to the sum of MoO3 and MoSZ when the XANES spectrum is
extracted from the spectrum of the regenerated hydrotreatment catalyst
obtained in the XAFS measurement by using an XAFS analysis
software of REX2000 (made by Rigaku), and then the pattern-fitting of
20 the-analysis software is carried out in a range of 19,990 eV to 20,050 eV
by using MoO3 and MoSZ measured under the same conditions as the
regenerated catalyst.
[0048] Also, the spectrum obtained by performing the XAFS analysis is
analyzed using an integrated XAFS analysis software of REX2000
25 (made by Rigaku), and details of data analysis such as a method of
taking a baseline for calculating the ratio of molybdenum oxide were
19
FP10-0588-00
performed using the integrated XAFS analysis software of REX2000
(made by Rigaku), according to methods disclosed in "78-79 pp., X-ray
absorption spectroscopy-XAFS and its applications-edited by Toshiaki
OTA and published by IPC (2002)" and instructions disclosed in "51-59
5 pp., Instruction manual of the integrated XAFS analysis software of
REX2000 (made by Rigaku)".
[0049] The XAFS analysis of the regenerated catalyst of the present
invention will be omitted herein because it is carried out under the same
conditions as the above-described analysis conditions.
10 [0050] Since the activity of an unused catalyst (new catalyst) varies by
catalyst manufacturer or manufacturing unit, it is considered appropriate
that the activity of the regenerated catalyst regenerated from the
hydrotreatment catalyst after it is used should be assessed through the
relative value to the activity of the unused catalyst corresponding
15 thereto. Herein, the activity of the regenerated catalyst is assessed
through specific activity defined in the following equation.
Specific activity=Desulfurization rate constant of regenerated
catalyst/Desulfurization rate constant of unused catalyst
[0051 ] (How to use regenerated catalyst)
20 Theregenerated catalyst of the present invention may be used alone as a
catalyst for the hydrotreatment process of the petroleum fraction, or
used by being stacked with an unused catalyst. In the cases of using
the regenerated catalyst stacked with an unused catalyst, the ratio of the
regenerated catalyst is not specifically limited, but is preferably 80 or
25 higher (mass ratio), and more preferably 120 or higher (mass ratio) with
respect to 100 of the unused catalyst in terms of reducing the amount of
20
FP1®-0588-00
waste catalyst and ease of catalyst separation during the replacement of
catalysts.
[Example]
[0052] Hereinafter, the present invention will be more fully described
5 with reference to Examples and Comparative Examples, but is not
limited whatsoever by these Examples presented below.
[0053] [Example 1]
(Regenerated catalyst)
A spent hydrotreatment catalyst which has been used for 2 years in a
10 hydrotreating facility for kerosene was prepared as shown in Table 1,
wherein the catalyst was obtained by supporting molybdenum and
cobalt as active metals on an alumina carrier. The spent hydrotreatment
catalyst was weighted out 5mg onto a pan made of platinum, then set in
a differential thermal analyzer (Thermo Plus 2 series/TG8110, made by
15 Rigaku Co., Ltd.), and a differential thermal analysis was carried out at
an air flow rate of 100 ml/min by raising the temperature by 10°C/min
from room temperature to 700°C. Thereafter, Ti and T2 were calculated
from the results of the differential thermal analysis according to the
aforesaid method, resulting in T1=250°C and T2=400°C. Here, the
20 spent hydrotreatment catalyst was regenerated for 4 hours at 350°C
(T1+100°C, T2-50°C) as shown in Table 1, thereby obtaining a
regenerated catalyst 1.
[0054] (Analysis of residual carbon in regenerated catalyst)
The measurement of a residual carbon content was performed on the
25 regenerated catalyst 1. The details of the analysis operation are the same
as described above, and the results are shown in Table 1.
21
FF10-0588-00
[0055] (XRD analysis of regenerated catalyst)
A small quantity of the regenerated catalyst 1 was powdered and an
XRD analysis was then carried out. The details of the analysis operation
are the same as described above. From the analysis results, a ratio of a
5 diffraction peak intensity (Hm) of 20=about 26.5° which was attributed
to a composite oxide CoMo®4, made of the active metals molybdenum
and cobalt, with respect to a diffraction peak intensity (Ha) of 2e=about
66.8° which was attributed to alumina, was calculated and the calculated
results are shown in Table 1.
10 [0056] (Analysis of EXAFS region by subjecting regenerated catalyst to
,XAFS analysis)
After small quantities of the regenerated catalyst 1 and a spent catalyst
corresponding to the regenerated catalyst 1 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
15 XAFS analysis was then carried out. Details of the analysis procedure
are the same as described above. Hs and Ho were respectively
calculated from the radial distribution curve obtained , and the calculated
results of a peak intensity ratio (Hs/Ho) are shown in Table 1.
[0057] (Analysis of XANES region by subjecting regenerated catalyst
20 to XAFS analysis)
After small quantities of the regenerated catalyst 1, an unused catalyst
corresponding to the regenerated catalyst 1, and a spent catalyst
corresponding to the regenerated catalyst 1 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
25 XAFS analysis was then carried out . Details of the analysis procedure
are the same as described above. A ratio of Mo ®3 was calculated by
22
FP l0-0588-00
synthesizing the spectra of Mo®3 and MoS2 from the absorption edge
spectrum obtained from the regenerated catalyst 1, and the calculated
results are shown in Table 1.
[0058] (Hydrotreatment reaction)
5 The regenerated catalyst 1 obtained through the regeneration was filled
into a fixed-bed continuous-flow reactor to subject the catalyst to
presulfiding treatment. 1 mass% of DMDS was added to a fraction
corresponding to kerosene having the properties specified in Table 1
based on the mass of the fraction, and was continuously supplied to the
10 catalyst for 48 hours. Afterwards, a hydrotreatment reaction was carried
,out under the conditions shown in Table 1 by using a fraction
corresponding to kerosene having properties specified in Table 1 as an
oil feed stock. The desulfurization rate constant was calculated from the
content of a sulfur component in the oil produced. Also, the
15 desulfurization rate constant was calculated by carrying out the same
reaction using an unused catalyst corresponding to the regenerated
catalyst 1, and then the specific activity of the regenerated catalyst 1
was calculated from the desulfurization rate constant. The rcsults are
shown in Table 1.
20 [0059] [Example 21
(Regenerated catalyst)
A spent hydrotreatment catalyst which has been used for 2 years in a
hydrotreating facility for gas oil was prepared as shown in Table 1,
wherein the catalyst was obtained by supporting molybdenum and
25 cobalt as active metals on an alumina carrier, and a differential thermal
analysis was carried out in the same manner as Example 1 to calculate
23
FP10m0588-00
Ti and T2, resulting in T1=260°C and T2=410°C. Here, the spent
hydrotreatment catalyst was regenerated for 4 hours at 300°C
(T1+40°C, T2-110°C) as shown in Table 1, thereby obtaining a
regenerated catalyst 2.
5 [0060] (Analysis of residual carbon in regenerated catalyst)
A measurement of residual carbon content was performed on the
regenerated catalyst 2. The details of the analysis operation are the same
as described above, and the results are shown in Table 1.
[0061 ] (XRD analysis of regenerated catalyst)
10 A small quantity of the regenerated catalyst 2 was powdered and an
XRD analysis was then carried out. The details of the analysis operation
are the same as described above. From the analysis results, a ratio of a
diffraction peak intensity (Hm) of 20=about 26.5° which was attributed
to a composite oxide COMo®4, made of the active metals molybdenum
15 and cobalt, with respect to a diffraction peak intensity (Ha) of 20=about
66.8° which was attributed to alumina, was calculated and the calculated
results are shown in Table 1.
[0062] (Analysis of EXAFS region by subjecting regenerated catalyst to
XAFS analysis)
20 After small quantities of the regenerated catalyst 1 and a spent catalyst
corresponding to the regenerated catalyst 1 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. Hs and He were
25 respectively calculated from the radial distribution curve obtained, and
the calculated results of a peak intensity ratio (Hs/Ho) are shown in
24
FP10-0555-00
Table 1.
[0063] (Analysis of XANES region by subjecting regenerated catalyst
to XAFS analysis)
After small quantities of the regenerated catalyst 2, an unused catalyst
5 corresponding to the regenerated catalyst 2, and a spent catalyst
corresponding to the regenerated catalyst 2 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of an analysis
procedure are the same as described above. A ratio of MoO3 was
10 calculated by synthesizing the spectra of Mo®3 and MoS2 from the
`absorption edge spectrum obtained from the regenerated catalyst 2, and
the calculated results are shown in Table 1.
[0064] (Hydrotreatment reaction)
A hydrotreatment reaction was carried out in the same manner as
15 Example 1 except for the conditions as shown in Table 1 by using a
fraction, corresponding to gas oil having properties specified in Table 1,
as an oil feed stock. The results of the specific activity are shown in
Table 1.
[0065] [Example 3]
20 (Regenerated catalyst)
A spent hydrotreatment catalyst which has been used for 1 year in a
hydrotreating facility of vacuum gas oil was prepared as shown in Table
1, wherein the catalyst was obtained by supporting molybdenum and
cobalt as active metals on an alumina carrier, and a differential thermal
25 analysis was carried out in the same manner as Example 1 to calculate
Ti and T2, resulting in Tl=10°C and T2=460°C. Here, the spent
25
FP10-0588-00
hydrotreatment catalyst was regenerated for 0 . 5 hours at 450°C
(T1+140°C, T2-10°C) as shown in Table 1, thereby obtaining a
regenerated catalyst 3.
[0066] (Analysis of residual carbon in regenerated catalyst)
5 The measurement of residual carbon content was performed on the
regenerated catalyst 3 . The details of the analysis operation are the same
as described above, and the results are shown in Table 1.
[0067] (XRD analysis of regenerated catalyst)
A small quantity of the regenerated catalyst 3 was powdered and an
10 XRD analysis was then carried out. The details of the analysis operation
are the same as described above. From the analysis results , a ratio of a
diffraction peak intensity (Hm) of 20=about 26.5° which was attributed
to a composite oxide CoMoO4, made of the active metals molybdenum
and cobalt, with respect to a diffraction peak intensity (Ha) of 20=about
15 66.8° which was attributed to alumina, was calculated and the calculated
results are shown in Table 1.
[0068] (Analysis of EXAFS region by subjecting regenerated catalyst to
XAFS analysis)
After small quantities of the regenerated catalyst 3 and a spent catalyst
20 corresponding to the regenerated catalyst 3 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. Hs and Ho were
respectively calculated from the radial distribution curve obtained, and
25 the calculated results of a peak intensity ratio (Hs/Ho) are shown in
Table 1.
26
FFIO-0588-00
[0069] (Analysis of XANES region by subjecting regenerated catalyst
to XAFS analysis)
After small quantities of the regenerated catalyst 3, an unused catalyst
corresponding to the regenerated catalyst 3, and a spent catalyst
5 corresponding to the regenerated catalyst 3 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. A ratio of Mo®3 was
calculated by synthesizing spectra of Mo®3 and MoS2 from the
10 absorption edge spectrum obtained from the regenerated catalyst 3, and
the calculated results are shown in Table 1.
[0070] (Hydrotreatment reaction)
A hydrotreatment reaction was carried out in the same manner as
Example 1 except for the conditions as shown in Table 1 by using a
15 fraction, corresponding to vacuum gas oil having properties specified in
Table 1, as an oil feed stock. The results of the specific activity are
shown in Table 1.
[0071] [Example 4]
(Regenerated catalyst)
20 A spent hydrotreatment catalyst which has been used for 1 year in a
hydrotreating facility for gas oil was prepared as shown in Table 1,
wherein the catalyst was obtained by supporting molybdenum and
cobalt as active metals on an alumina carrier, and a differential thermal
analysis was carried out in the same manner as Example 1 to calculate
25 Ti and T2, resulting in T1=360°C and T2=390°C. Here, the spent
hydrotreatment catalyst was regenerated for 4 hours at 400°C
27
FP1O-0588-00
(T1+40°C, T2+10°C) as shown in Table 1, thereby obtaining a
regenerated catalyst 4.
[0072] (Analysis of residual carbon in regenerated catalyst)
The measurement of residual carbon content was performed on the
5 regenerated catalyst 4. The details of the analysis operation are the same
as described above, and the results are shown in Table 1.
[0073] (XRD analysis of regenerated catalyst)
A small quantity of the regenerated catalyst 4 was powdered and an
XRD analysis was then carried out. The details of the analysis operation
10 are the same as described above. From the analysis results, a ratio of a
'diffraction peak intensity (Hm) of 20=about 26.5° which was attributed
to a composite oxide CoMo®4, made of the active metals molybdenum
and cobalt, with respect to a diffraction peal-, intensity (Ha) of 20=about
66.8° which was attributed to alumina, was calculated and the calculated
15 results are shown in Table 1.
[0074] (Analysis of EXAFS region by subjecting regenerated catalyst to
XAFS analysis)
After small quantities of the regenerated catalyst 4 and a spent catalyst
corresponding to the regenerated catalyst 4 were respectively powdered,
20 the -powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. Hs and Ho were
respectively calculated from the radial distribution curve obtained, and
the calculation results of a peak intensity ratio (Hs/Ho) are shown in
25 Table 1.
[0075] (Analysis of XANES region by subjecting regenerated catalyst
28
FP10a0588-00
to XAFS analysis)
After small quantities of the regenerated catalyst 4, an unused catalyst
corresponding to the regenerated catalyst 4, and a spent catalyst
corresponding to the regenerated catalyst 4 were respectively powdered,
5 the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. A ratio of MoO3 was
calculated by synthesizing the spectra of MoO3 and MoS2 from the
absorption edge spectrum obtained from the regenerated catalyst 4, and
10 the calculated results are shown in Table 1.
[0076] (Hydrotreatment reaction)
A hydrotreatment reaction was carried out in the same manner as
Example 1 except for the conditions as shown in Table 1 by using a
fraction, corresponding to gas oil having properties specified in Table 1,
15 as an oil feed stock. The results of the specific activity are shown in
Table 1.
[0077] [Comparative Example 1]
(Regenerated catalyst)
A spent hydrotreatment catalyst which has been used for 2 years in a
20 hydrotreating facility for kerosene was prepared as shown in Table 1,
wherein the catalyst was obtained by supporting molybdenum and
cobalt as active metals on an alumina carrier, and a differential thermal
analysis was carried out in the same manner as Example 1 to calculate
Tl and T2, resulting in T1=250°C and T2=310°C. Here, the spent
25 hydrotreatment catalyst was regenerated for 10 hours at 350°C
(T1+100°C, T2+40°C) as shown in Table 1, thereby obtaining a
29
FP10-0588-00
regenerated catalyst 5.
[0078] (Analysis of residual carbon in regenerated catalyst)
The measurement of residual carbon content was performed on the
regenerated catalyst 5. The details of the analysis operation are the same
5 as described above, and the results are shown in Table 1.
[0079] (XRD analysis of regenerated catalyst)
A small quantity of the regenerated catalyst 5 was powdered and an
XRD analysis was then carried out. The details of the analysis operation
are the same as described above. From the analysis results, a ratio of a
10 diffraction peak intensity (Hm) of 20=about 26.5° which was attributed
'to a composite oxide CoMoO4, made of the active metals molybdenum
and cobalt, with respect to a diffraction peak intensity (Ha) of 29=about
66.8° which was attributed to alumina, was calculated and the calculated
results are shown in Table 1.
15 [0080] (Analysis of EXAFS region by subjecting regenerated catalyst to
XAFS analysis)
After small quantities of the regenerated catalyst 5 and a spent catalyst
corresponding to the regenerated catalyst 5 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
20 XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. Hs and Ho were
respectively calculated from the radial distribution curve obtained, and
the calculated results of a peak intensity ratio (Hs/Ho) are shown in
Table 1.
25 [0081] (Analysis of XANES region by subjecting regenerated catalyst
to XAFS analysis)
30
FP10-0588-00
After small quantities of the regenerated catalyst 5, an unused catalyst
corresponding to the regenerated catalyst 5, and a spent catalyst
corresponding to the regenerated catalyst 5 were respectively powdered,
the powdered catalysts were tableted to form pellet -like objects and the
5 XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. A ratio of MoO3 was
calculated by synthesizing the spectra of MoO3 and MoS2 from the
absorption edge spectrum obtained from the regenerated catalyst 5, and
the calculated results are shown in Table 1.
10 [0082] (Hydrotreatment reaction)
A hydrotreatment reaction was carried out in the same manner as
Example 1 except for the conditions as shown in Table 1 by using a
fraction, corresponding to kerosene having properties specified in Table
1, as an oil feed stock. The results of the specific activity are shown in
15 Table 1.
[0083] [Comparative Example 2]
(Regenerated catalyst)
A spent hydrotreatment catalyst which has been used for 2 years in a
hydrotreating facility for gas oil was prepared as shown in Table 1,
20 wherein the catalyst was obtained by supporting molybdenum and
cobalt as active metals on an alumina carrier, and a differential thermal
analysis was carried out in the same manner as Example 1 to calculate
Ti and T2, resulting in T1=310°C and T2=410°C. Here, the spent
hydrotreatment catalyst was regenerated for 5 hours at 200°C
25 (T1-110°C, T2-210°C) as shown in Table 1, thereby obtaining a
regenerated catalyst 6.
31
FP10-0588-00
[0084] (Analysis of residual carbon in regenerated catalyst)
The measurement of residual carbon content was performed on the
regenerated catalyst 6. The details of the analysis operation are the same
as described above, and results are shown in Table 1.
5 [0085] (XRD analysis of regenerated catalyst)
A small quantity of the regenerated catalyst 6 was powdered and an
XRD analysis was then carried out. Details of the analysis operation are
the same as described above. From the analysis results, a ratio of a
diffraction peak intensity (Hm) of 20=about 26.5° which was attributed
10 to a composite oxide CoMo®4, made of the active metals molybdenum
and cobalt, with respect to a diffraction peak intensity (Ha) of 20=about
66.5° which was attributed to alumina, was calculated and the calculated
results are shown in Table 1.
[0086] (Analysis of EXAFS region by subjecting regenerated catalyst to
15 XAFS analysis)
After small quantities of the regenerated catalyst 6 and a spent catalyst
corresponding to the regenerated catalyst 6 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
20 procedure are the same as described above. Hs and Ho were
respectively calculated from the radial distribution curve obtained, and
the calculated results of a peak intensity ratio (Hs/Ho) are shown in
Table 1.
[0087] (Analysis of XANES region by subjecting regenerated catalyst
25 to XAFS analysis)
After small quantities of the regenerated catalyst 6, an unused catalyst
32
FP1O-0588-00
corresponding to the regenerated catalyst 6, and a spent catalyst
corresponding to the regenerated catalyst 6 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
5 procedure are the same as described above. A ratio of MoO3 was
calculated by synthesizing the spectra of MoO3 and MoS2 from the
absorption edge spectrum obtained from the regenerated catalyst 6, and
the calculated results are shown in Table 1.
[0088] (Hydrotreatment reaction)
10 A hydrotreatment reaction was carried out in the same manner as
Example 1 except for the conditions as, shown in Table 1 by using a
fraction, corresponding to gas oil having properties specified in Table 1,
as an oil feed stock. The results of the specific activity are shown in
Table 1.
15 [0089] [Comparative Example 3]
(Regenerated catalyst)
A spent hydrotreatment catalyst which has been used for 1 year in a
hydrotreating facility for vacuum gas oil was prepared as shown in
Table 1, wherein the catalyst was obtained by supporting molybdenum
20 and. cobalt as active metals on an alumina carrier, and a differential
thermal analysis was carried out in the same manner as Example 1 to
calculate Ti and T2, resulting in T1=440°C and T2=500°C. Here, the
spent hydrotreatment catalyst was regenerated for 4 hours at 400°C
(Tl-40°C, T2-100°C) as shown in Table 1, thereby obtaining a
25 regenerated catalyst 7.
[0090] (Analysis of residual carbon in regenerated catalyst)
33
FP1O-0588-00
The measurement of residual carbon content was performed on the
regenerated catalyst 7. The details of the analysis operation are the same
as described above, and the results are shown in Table 1.
[0091] (XRD analysis of regenerated catalyst)
5 A small quantity of the regenerated catalyst 7 was powdered and an
XRD analysis was then carried out . The details of the analysis operation
are the same as described above. From the analysis results, a ratio of a
diffraction peak intensity (Hm) of 28=about 26 . 5° which was attributed
to a composite oxide CoM0®4, made of the active metals molybdenum
10 and cobalt, with respect to a diffraction peak intensity (Ha) of 20=about
66.8° which was attributed to alumina, was calculated and the calculated
results are shown in Table 1.
[0092] (Analysis of EXAFS region by subjecting regenerated catalyst to
XAFS analysis)
15 After small quantities of the regenerated catalyst 7 and a spent catalyst
corresponding to the regenerated catalyst 7 were respectively powdered,
the powdered catalysts were tableted to form pellet -like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. Hs and Ho were
20 respectively calculated from the radial distribution curve obtained, and
the calculated results of a peak intensity ratio (Hs/Ho ) are shown in
Table 1.
[0093 ] (Analysis of XANES region by subjecting regenerated catalyst
to XAFS analysis)
25 After small quantities of the regenerated catalyst 7, an unused catalyst
corresponding to the regenerated catalyst 7 , and a spent catalyst
34
FP10-0588-00
corresponding to the regenerated catalyst 7 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. A ratio of MoO3 was
5 calculated by synthesizing the spectra of MoO3 and MoS2 from the
absorption edge spectrum obtained from the regenerated catalyst 7, and
the calculated results are shown in Table 1.
[0094] (Hydrotreatment reaction)
A hydrotreatment reaction was carried out in the same manner as
10 Example 1 except for the conditions as shown in Table 1 by using a
fraction, corresponding to vacuum gas oil having properties specified in
Table 1, as an oil feed stock. The results of the specific activity are
shown in Table 1.
[0095] [Comparative Example 4]
15 (Regenerated catalyst)
A spent hydrotreatment catalyst which has been used for 1 year in a
hydrotreating facility for gas oil was prepared as shown in Table 1,
wherein the catalyst was obtained by supporting molybdenum and
cobalt as active metals on an alumina carrier, and a differential thermal
20 analysis was carried out in the same manner as Example 1 to calculate
T1 and T2, resulting in T1=310°C and T2=410°C. Here, the spent
hydrotreatment catalyst was regenerated for 4 hours at 500°C
(T1+190°C, T2+90°C) as shown in Table 1, thereby obtaining a
regenerated catalyst 8.
25 [0096] (Analysis of residual carbon in regenerated catalyst)
The measurement of residual carbon content was performed on the
35
FP1o-0588-00
regenerated catalyst 8. The details of the analysis operation are the same
as described above, and the results are shown in Table 1.
[0097] (XRD analysis of regenerated catalyst)
A small quantity of the regenerated catalyst 8 was powdered and an
5 XRD analysis was then carried out. The details of the analysis operation
are the same as described above. From the analysis results, a ratio of a
diffraction peak intensity (Hm) of 20=about 26.5° which was attributed
to a composite oxide CoMo®4, made of the active metals molybdenum
and cobalt, with respect to a diffraction peak intensity (Ha) of 20=about
10 66.8° which was attributed to alumina, was calculated and the calculated
results are shown in Table 1.
[0098] (Analysis of EXAFS region by subjecting regenerated catalyst to
XAFS analysis)
After small quantities of the regenerated catalyst 8 and a spent catalyst
15 corresponding to the regenerated catalyst 8 were respectively powdered,
the powdered catalysts were tableted to form pellet-like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above. Hs and 1 to were
respectively calculated from the radial distribution curve obtained, and
20 the. calculated results of a peak intensity ratio (Hs/Ho) are shown in
Table 1.
[0099] (Analysis of XANES region by subjecting regenerated catalyst
to XAYS analysis)
After small quantities of the regenerated catalyst 8, an unused catalyst
25 corresponding to the regenerated catalyst 8, and a spent catalyst
corresponding to the regenerated catalyst 8 were respectively powdered,
36
FP1®-0555-00
the powdered catalysts were tableted to form pellet -like objects and the
XAFS analysis was then carried out. The details of the analysis
procedure are the same as described above . A ratio of M0O3 was
calculated by synthesizing the spectra of M003 and MoS2 from the
5 absorption edge spectrum obtained from the regenerated catalyst 8, and
the calculated results are shown in Table 1.
[0100] (Hydrotreatment reaction)
A hydrotreatment reaction was carried out in the same manner as
Example 1 except for the conditions as shown in Table 1 by using a
10 fraction, corresponding to gas oil having properties specified in Table 1,
as an oil feed stock. The results of the specific activity are shown in
Table 1.
[Table 1]
37
FP1O-0588-00
Example Comparative Example
1 2 3 4 2 3 4
Reg. Reg. Reg, Reg. Reg. Reg. Reg. Reg.
Catalyst Name
Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4 Ca Catalyst 6 Catalyst 7 Catalyst 8
Kerosene Gas oil
Vacuum
Gas oil Ke Gas oil
Vacuum
Gas oil
Hydrotreatment facility gas oil
J
using catalyst treating treating
treating
treating tr treating
treating
treating
facility facility facility f facility facility
facility Facilit
Service life (years) 2 2 1 1 2 1 1
m Residual carbon content (mass%) 1.5 1.8 1.0 0 . 2 4 0,10 0.08
,
U
Peak intensity ratio Hm /Ha of XRD 0.83 0.85 1.09 0. 95 0.80 0.59 1.43 1.75
Peak intensity ratio Hs/Ho of
0.16 0.38 0.17 0.19 0.09 0.71 0 17 0 04
EXAFS radial distribution curve
, .
MoO3 ratio (%) of
93 87 90 98 94 70 99 100
XANES absorption edge spectrum
TI C C) 250 260 310 360 250 310 440 310
o T2C C) 400 410 460 390 310 410 500 410
m 'N 350 300 450 400 350 200 400 500
Temperature of regeneration process
U
(.
C)
(T1+100) (T1+40) (T1+140) (T1+40) (T1+100) (T1-110) (T1-40) (T1+190)
(T2-50) (T2-110) (T2-10) (T2+10) (T2+40) (T2-210) (T2-100) (T2+90)
Regeneration time (h) 4 4 0.5 4 10 5 4 4
Name of Oil feed Oil feed Oil feed Oil feed Oil feed Oil feed Oil feed Oil feed
Oil feed stock stock I stock 2 stock 3 stock 2 stock 1 stock 2 stock 3 stock 2
c v Density (k /m3) 799.4 851 . 6 923.6 851.6 799.4 851.6 923 . 6 851.6
;o
0
Initial boiling point
o °m C C)
152 231 274 231 152 231 274 231
U .: Final boiling point
c
m 0 (. L,) 270 376 635 376 270 376 635 376
E
Sulfur component
0.25 1.18 2.16 1.18 0 . 25 1.18 2.18 1,18
0
(mass%)
Hydrogen partial pressure (MPa) 3 6 8 6 3 6 6 6
LHSV (0) 2 1 1 1 2 1 1 1
Hydrogen / oil ratio (SCF/BBL) 700 1000 3000 1000 700 1000 3000 1000
Reaction temperature (° C) 300 380 380 380 300 380 380 380
Specific Activity
(Relative value assuming unused catalyst is 1) 0.866 0.978 0.960 0.935 0.898 0.880 0.873 0.853
[0101] From the results of Table 1, it is found that as the residual carbon
content, and the results of XRD analysis and XAFS analysis fall within
an applicable range, the regenerated catalyst of the present invention has
an activity of about 93% or more as a relative value to an activity of an
5 unused catalyst (Examples 1 to 4). On the contrary, as illustrated in
Comparative Examples 5 to 8, in any case where one of the analysis
items deviates from the applicable range, the regenerated catalyst has an
activity of about 90% or less as a relative value to an activity of an
unused catalyst, and thus, the activity is significantly lowered.
10
38
FP1O-0588-00

CLAIMS
1. A regenerated hydrotreatment catalyst regenerated from a
hydrotreatment catalyst for treating a petroleum fraction, the
hydrotreatment catalyst being prepared by supporting molybdenum and
5 at least one species selected from metals of Groups 8 to 10 of the
Periodic Table on an inorganic carrier containing an aluminum oxide,
wherein,
a residual carbon content is in the range of 0.15 mass% to 3.0
mass%,
10 a peak intensity of a molybdenum composite metal oxide with
respect to an intensity of a base peak is in the range of 0.60 to 1.10 in an
X-Ray diffraction spectrum, and
a peak intensity of a Mo-S bond derived from a residual sulfur
peak with respect to an intensity of a base peak is in the range of 0.10 to
15 0.60 in a radial distribution curve obtained from an extended X-ray
absorption fine structure spectrum of an X-ray absorption fine structure
analysis.
2. A regenerated hydrotreatment catalyst regenerated from a
hydrotreatment catalyst for treating a petroleum fraction, the
20 hydrotreatment catalyst being prepared by supporting molybdenum and
at least one species selected from metals of Groups 8 to 10 of the
Periodic Table on an inorganic carrier containing an aluminum oxide,
wherein,
a residual carbon content is in the range of 0.15 mass% to 3.0
25 mass%,
a peak intensity of a molybdenum composite metal oxide with
39
FP10-0588-00
respect to an intensity of a base peak is in the range of 0.60 to 1.10 in an
X-Ray diffraction spectrum, and
a ratio of M0®3 is in the range of 77% to 99% in an X-ray
absorption near-edge structure spectrum of an X-ray absorption fine
5 structure analysis.
3. A method of manufacturing a petroleum product, wherein
hydrotreatment of a petroleum fraction is performed using the
regenerated hydrotreatment catalyst according to claim 1 or 2.
4. The method according to claim 3, wherein conditions of the
10 hydrotreatment of the petroleum fraction are a hydrogen partial pressure
in the range of .3 to 13 MPa, LHSV in the range of 0.05 to 5 h4, a
reaction temperature in the range of 200°C to 410°C, a hydrogen/oil
ratio in the range of 100 to 8,000 SCF/BBL, and a boiling point in the
range of 130°C to 700°C of the petroleum fraction used as an oil feed
15 stock.